Stranski–Krastanov

growth

Stranski–Krastanov growth (SK growth,

also Stransky-Krastanov or Stranski-
Krastanow) is one of the three primary
modes by which thin films grow epitaxially
at a crystal surface or interface. Also
known as 'layer-plus-island growth', the SK
mode follows a two step process: initially,
complete films of adsorbates, up to
several monolayers thick, grow in a layer-
by-layer fashion on a crystal substrate.
Beyond a critical layer thickness, which
depends on strain and the chemical
potential of the deposited film, growth
continues through the nucleation and
coalescence of adsorbate 'islands'.[1][2][3][4]
This growth mechanism was first noted by
Ivan Stranski and Lyubomir Krastanov in
1938.[5] It wasn’t until 1958 however, in a
seminal work by Ernst Bauer published in
Zeitschrift für Kristallographie, that the SK,
Volmer-Weber, and Frank–van der Merwe
mechanisms were systematically
classified as the primary thin-film growth
processes.[6] Since then, SK growth has
been the subject of intense investigation,
not only to better understand the complex
thermodynamics and kinetics at the core
of thin-film formation, but also as a route
to fabricating novel nanostructures for
application in the microelectronics
industry.

Modes of thin-film growth

Figure 1. Cross-section views of the three primary

modes of thin-film growth including (a) Volmer–Weber
(VW: island formation), (b) Frank–van der Merwe (FM:
layer-by-layer), and (c) Stranski–Krastanov (SK: layer-
plus-island). Each mode is shown for several different
amounts of surface coverage, Θ.

The growth of epitaxial (homogeneous or

heterogeneous) thin films on a single
crystal surface depends critically on the
interaction strength between adatoms and
the surface. While it is possible to grow
epilayers from a liquid solution, most
epitaxial growth occurs via a vapor phase
technique such as molecular beam epitaxy
(MBE). In Volmer–Weber (VW) growth,
adatom–adatom interactions are stronger
than those of the adatom with the surface,
leading to the formation of three-
dimensional adatom clusters or islands.[3]
Growth of these clusters, along with
coarsening, will cause rough multi-layer
films to grow on the substrate surface.
Antithetically, during Frank–van der Merwe
(FM) growth, adatoms attach preferentially
to surface sites resulting in atomically
smooth, fully formed layers. This layer-by-
layer growth is two-dimensional, indicating
that complete films form prior to growth of
subsequent layers.[2][3] Stranski–
Krastanov growth is an intermediary
process characterized by both 2D layer
and 3D island growth. Transition from the
layer-by-layer to island-based growth
occurs at a critical layer thickness which is
highly dependent on the chemical and
physical properties, such as surface
energies and lattice parameters, of the
substrate and film.[1][2][3] Figure 1 is a
schematic representation of the three
main growth modes for various surface
coverages.

Determining the mechanism by which a

thin film grows requires consideration of
the chemical potentials of the first few
deposited layers.[2][7] A model for the layer
chemical potential per atom has been
proposed by Markov as:[7]
where is the bulk chemical potential
of the adsorbate material, is the
desorption energy of an adsorbate atom
from a wetting layer of the same material,
the desorption energy of an
adsorbate atom from the substrate,
is the per atom misfit dislocation energy,
and the per atom homogeneous
strain energy. In general, the values of ,
, , and depend in a
complex way on the thickness of the
growing layers and lattice misfit between
the substrate and adsorbate film. In the
limit of small strains, , the
criterion for a film growth mode is

dependent on .

VW growth: (adatom cohesive

force is stronger than surface adhesive

force)

FM growth: (surface adhesive

force is stronger than adatom cohesive

force)

SK growth can be described by both of

these inequalities. While initial film growth
follows a FM mechanism, i.e. positive
differential μ, nontrivial amounts of strain
energy accumulate in the deposited layers.
At a critical thickness, this strain induces a
sign reversal in the chemical potential, i.e.
negative differential μ, leading to a switch
in the growth mode. At this point it is
energetically favorable to nucleate islands
and further growth occurs by a VW type
mechanism.[7] A thermodynamic criterion
for layer growth similar to the one
presented above can be obtained using a
force balance of surface tensions and
contact angle.[8]
Figure 2. SK growth
showing island formation
after obtaining a critical
thickness, . Lines
represent lattice planes with
thicker lines for the
substrate lattice and thinner
lines for the growing film.
Edge dislocations are
highlighted in red at the
film/island interface.

Figure 3. Coherent island

formation under SK growth.
Local curvature of the near
 surface region surrounding
the island leads to elastic
deformation of the island
and wetting layer thereby
reducing the accumulated
strain. These islands are
defect free.

Since the formation of wetting layers

occurs in a commensurate fashion at a
crystal surface, there is often an
associated misfit between the film and the
substrate due to the different lattice
parameters of each material. Attachment
of the thinner film to the thicker substrate
induces a misfit strain at the interface
given by . Here and are

the film and substrate lattice constants,

respectively. As the wetting layer thickens,
the associated strain energy increases
rapidly. In order to relieve the strain, island
formation can occur in either a dislocated
or coherent fashion. In dislocated islands,
strain relief arises by forming interfacial
misfit dislocations. The reduction in strain
energy accommodated by introducing a
dislocation is generally greater than the
concomitant cost of increased surface
energy associated with creating the
clusters. The thickness of the wetting layer
at which island nucleation initiates, called
the critical thickness , is strongly
dependent on the lattice mismatch
between the film and substrate, with a
greater mismatch leading to smaller
critical thicknesses.[9] Values of can
range from submonlayer coverage to up to
several monolayers thick.[1][10] Figure 2
illustrates a dislocated island during SK
growth after reaching a critical layer
height. A pure edge dislocation is shown
at the island interface to illustrate the
relieved structure of the cluster.

In some cases, most notably the Si/Ge

system, nanoscale dislocation-free islands
can be formed during SK growth by
introducing undulations into the near
surface layers of the
substrate.[11][12][13][14][10] These regions of
local curvature serve to elastically deform
both the substrate and island, relieving
accumulated strain and bringing the
wetting layer and island lattice constant
closer to its bulk value. This elastic
instability at is known as the Grinfeld
instability (formerly Asaro–Tiller–Grinfeld;
ATG).[7] The resulting islands are coherent
and defect-free, garnering them significant
interest for use in nanoscale electronic
and optoelectronic devices. Such
applications are discussed briefly later. A
schematic of the resulting epitaxial
structure is shown in figure 3 which
highlights the induced radius of curvature
at the substrate surface and in the island.
Finally, it should be noted that strain
stabilization indicative of coherent SK
growth decreases with decreasing inter-
island separation. At large areal island
densities (smaller spacing), curvature
effects from neighboring clusters will
cause dislocation loops to form leading to
defected island creation.[11]

Monitoring SK growth
Wide beam techniques
Figure 4. Evolution of Auger peak height as function of
surface coverage during SK growth. The plot is a series
of segmented linear curves with a clear break point
indicating the critical thickness (clearly marked in the
diagram) and the onset of island growth. Slope
differences are due to the different modes of growth.
The initial steep-sloped segment corresponds to the
FM growth mode while the later, shallow-sloped region
is representative of the VW mode. This schematic is
characteristic of 'ideal' SK growth where nucleation
onset begins at 2 monolayer coverage.

Analytical techniques such as Auger

electron spectroscopy (AES), low-energy
electron diffraction (LEED), and reflection
high energy electron diffraction (RHEED),
have been extensively used to monitor SK
growth. AES data obtained in situ during
film growth in a number model systems,
such as Pd/W(100), Pb/Cu(110),
Ag/W(110), and Ag/Fe(110), show
characteristic segmented curves like those
presented in figure 4.[1][2][11] Height of the
film Auger peaks plotted as a function of
surface coverage Θ, initially exhibits a
straight line, which is indicative of AES
data for FM growth. There is a clear break
point at a critical adsorbate surface
coverage followed by another linear
segment at a reduced slope. The paired
break point and shallow line slope is
characteristic of island nucleation; a
similar plot for FM growth would exhibit
many such line and break pairs while a
plot of the VW mode would be a single line
of low slope. In some systems,
reorganization of the 2D wetting layer
results in decreasing AES peaks with
increasing adsorbate coverage.[11] Such
situations arise when many adatoms are
required to reach a critical nucleus size on
the surface and at nucleation the resulting
adsorbed layer constitutes a significant
fraction of a monolayer. After nucleation,
metastable adatoms on the surface are
incorporated into the nuclei, causing the
Auger signal to fall. This phenomenon is
particularly evident for deposits on a
molybdenum substrate.

Evolution of island formation during a SK

transitions have also been successfully
measured using LEED and RHEED
techniques. Diffraction data obtained via
various LEED experiments have been
effectively used in conjunction with AES to
measure the critical layer thickness at the
onset of island formation.[2][11] In addition,
RHEED oscillations have proven very
sensitive to the layer-to-island transition
during SK growth, with the diffraction data
providing detailed crystallographic
information about the nucleated islands.
Following the time dependence of LEED,
RHEED, and AES signals, extensive
information on surface kinetics and
thermodynamics has been gathered for a
number of technologically relevant
systems.

Microscopies

Unlike the techniques presented in the last

section in which probe size can be
relatively large compared to island size,
surface microscopies such scanning
electron microscopy (SEM), transmission
electron microscopy (TEM), scanning
tunneling microscopy (STM), and Atomic
force microscopy (AFM) offer the
opportunity for direct viewing of
deposit/substrate combination
events.[1][3][11] The extreme magnifications
afforded by these techniques, often down
to the nanometer length scale, make them
particularly applicable for visualizing the
strongly 3D islands. UHV-SEM and TEM
are routinely used to image island
formation during SK growth, enabling a
wide range of information to be gathered,
ranging from island densities to
equilibrium shapes.[1][2][3] AFM and STM
have become increasingly utilized to
correlate island geometry to the surface
morphology of the surrounding substrate
and wetting layer.[14] These visualization
tools are often used to complement
quantitative information gathered during
wide-beam analyses.

Application to
nanotechnology
As mentioned previously, coherent island
formation during SK growth has attracted
increased interest as a means for
fabricating epitaxial nanoscale structures,
particularly quantum dots
(QDs).[12][13][14][15][16] Significant effort has
been spent developing methods to control
island organization, density, and size on a
substrate. Techniques such as surface
dimpling with a pulsed laser and control
over growth rate have been successfully
applied to alter the onset of the SK
transition or even suppress it
altogether.[14][17] The ability to control this
transition either spatially or temporally
enables manipulation of physical
parameters of the nanostructures, like
geometry and size, which, in turn, can alter
their electronic or optoelectronic
properties (i.e. band gap). For example,
Schwarz-Selinger, et al. have used surface
dimpling to create surface miscuts on Si
that provide preferential Ge island
nucleation sites surrounded by a denuded
zone.[14] In a similar fashion,
lithographically patterned substrates have
been used as nucleation templates for
SiGe clusters.[13][15] Several studies have
also shown that island geometries can be
altered during SK growth by controlling
substrate relief and growth rate.[14][16]
Bimodal size distributions of Ge islands on
Si are a striking example of this
phenomenon in which pyramidal and
dome-shaped islands coexist after Ge
growth on a textured Si substrate.[14] Such
ability to control the size, location, and
shape of these structures could provide
invaluable techniques for 'bottom-up'
fabrication schemes of next-generation
devices in the microelectronics industry.

See also
Epitaxy
Thin films
Molecular-beam epitaxy

References
1. Venables, John (2000). Introduction to
Surface and Thin Film Processes.
Cambridge: Cambridge University Press.
ISBN 0-521-62460-6.
2. Pimpinelli, Alberto; Jacques Villain
(1998). Physics of Crystal Growth.
Cambridge: Cambridge University Press.
ISBN 0-521-55198-6.
3. Oura, K.; V.G. Lifshits; A.A. Saranin; A.V.
Zotov; M. Katayama (2003). Surface
Science: An Introduction. Berlin: Springer.
ISBN 3-540-00545-5.
4. Eaglesham, D.J.; M. Cerullo (April 1990).
"Dislocation-free Stranski-Krastanow growth
of Ge on Si(100)". Physical Review Letters.
64 (16): 1943–1946.
Bibcode:1990PhRvL..64.1943E .
doi:10.1103/PhysRevLett.64.1943 .
PMID 10041534 .
5. Stranski, Ivan N.; Krastanow, Lubomir
(1938). "Zur Theorie der orientierten
Ausscheidung von Ionenkristallen
aufeinander". Abhandlungen der
Mathematisch-Naturwissenschaftlichen
Klasse IIb. Akademie der Wissenschaften
Wien. 146: 797–810.
6. Bauer, Ernst (1958). "Phänomenologische
Theorie der Kristallabscheidung an
Oberflächen. I". Zeitschrift für
Kristallographie. 110: 372–394.
Bibcode:1958ZK....110..372B .
doi:10.1524/zkri.1958.110.1-6.372 .
7. Markov, Ivan V. (1995). Crystal Growth for
Beginners: Fundamentals of Nucleation,
Crystal Growth, and Epitaxy. Singapore:
World Scientific. ISBN 981-02-1531-2.
8. See for example Oura et al (Surface
Science) or Venables (Introduction to
Surface and Thin Film Processes).
9. Matthews, John Wauchope (1975).
Epitaxial Growth. New York: Academic
Press. ISBN 0-12-480901-4.
10. Kukta, R.V.; L.B. Freund (November–
December 1997). "Minimum energy
configuration of epitaxial material clusters
on a lattice-mismatched substrate". Journal
of the Mechanics and Physics of Solids. 45
(11–12): 1835–1860.
Bibcode:1997JMPSo..45.1835K .
doi:10.1016/S0022-5096(97)00031-8 .
11. Venables, John; G. D. T. Spiller; M.
Hanbucken (April 1984). "Nucleation and
growth of thin films". Reports on Progress
in Physics. 47 (4): 399–459.
Bibcode:1984RPPh...47..399V .
doi:10.1088/0034-4885/47/4/002 .
12. Li, Y.R.; Z. Liang; Y. Zhang; J. Zhu; S.W.
Jiang; X.H. Wei (October 2005). "Growth
modes transition induced by strain
relaxation in epitaxial MgO thin films on
SrTiO3 (001) substrates". Thin Solid Films.
489 (1–2): 245–250.
Bibcode:2005TSF...489..245L .
doi:10.1016/j.tsf.2005.04.095 .
13. Chiu, C.-h.; Z. Huang; C. T. Poh
(September 2004). "Formation of
Nanostructures by the Activated Stranski-
Krastanow Transition Method". Physical
Review Letters. 93 (13): 36105.
Bibcode:2004PhRvL..93m6105C .
doi:10.1103/PhysRevLett.93.136105 .
PMID 15524741 .
14. Schwarz-Selinger, T.; Y. L. Foo; David G.
Cahill; J. E. Greene (March 2002). "Surface
mass transport and island nucleation during
growth of Ge on laser textured Si(001)".
Physical Review B. 53 (12): 125317.
Bibcode:2002PhRvB..65l5317S .
doi:10.1103/PhysRevB.65.125317 .
15. Bauer, G.; F. Schäffler (November 2006).
"Self-assembled Si and SiGe
nanostructures: New growth concepts and
structural analysis physica status solidi (a)".
Physica Status Solidi. 203 (14): 3496–3505.
Bibcode:2006PSSAR.203.3496B .
doi:10.1002/pssa.200622405 .
16. Shklyaev, O.E.; M. J. Beck; M. Asta; M. J.
Miksis; P. W. Voorhees (May 2005). "Role of
Strain-Dependent Surface Energies in
Ge/Si(100) Island Formation". Physical
Review Letters. 94 (17): 176102.
Bibcode:2005PhRvL..94q6102S .
doi:10.1103/PhysRevLett.94.176102 .
PMID 15904314 .
17. Watanabe, Fumiya; David G. Cahill; J. E.
Greene (February 2005). "Roughening Rates
of Strained-Layer Instabilities". Physical
Review Letters. 94 (6): 066101.
Bibcode:2005PhRvL..94f6101W .
doi:10.1103/PhysRevLett.94.066101 .
PMID 15783751 .
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